ph-sensitive sacrificial materials for the microfabrication of structures

Patent metadata

Field	Value
Publication number	US-9458357-B2
Application number	US-201213410600-A
Country	US
Kind code	B2
Filing date	Mar 2, 2012
Priority date	Mar 2, 2011
Publication date	Oct 4, 2016
Grant date	Oct 4, 2016

Abstract

Methods for microfabricating composite materials and composite materials prepared there from are described herein. The sacrificial material can be etched or patterned to create a two-dimensional and/or three-dimensional sacrificial material structure. The resulting sacrificial material structure can be embedded in one or more embedding materials. The sacrificial material(s) are materials whose solubility can be altered by application of a stimulus typically pH, and/or temperature, light, pH, pressure, presence of absence of ions, and combinations thereof. The embedding materials can contain one or more additives that modify one or more properties of the embedding materials, such as degradation properties, porosity, mechanical properties, viscosity, conductive properties, and combinations thereof. The composite materials can be used in tissue engineering, drug screening, toxin detection, drug delivery, filtrations, bioseparations, and as microfluidic devices for fluid mixing and structural repair.

First claim

We claim:

1. A method of microfabrication of a composite structure having one or more well defined, reproducible two dimensional and/or three dimensional structures, features, or channels each having sizes between nanometers and centimeters comprising
patterning or etching a sacrificial material formed from a first polymer to form a patterned sacrificial material structure, wherein the patterning or etching of the sacrificial material comprises a method selected from the group consisting of lithographic patterning, melt-spinning, wet-spinning, electrospinning, spin-coating, three dimensional printing, robotically controlled deposition, laser etching, plasma or chemical etching, stereolithography, selective laser sintering, ballistic particle manufacture, fusion deposition modeling, surface micromachining, bulk micromachining, and combinations thereof,
embedding the patterned sacrificial material structure in a polymeric embedding material to form an embedded sacrificial material structure,
wherein the patterned or etched first polymer is insoluble in a first solvent at a first pH and soluble in the first solvent upon a change from the first pH to a second different pH,
contacting the embedded sacrificial material structure with a bath comprising the first solvent at the first pH; and
changing the first pH of the first solvent to the second different pH, wherein the first polymer is solubilized in the first solvent at the second different pH,
wherein the polymeric embedding material is not soluble in the first solvent at the second different pH, and
removing the solubilized first polymer,
wherein the removal of the first polymer forms the structures, features, or channels, having the pattern of the patterned sacrificial material structure, within the polymeric embedding material.

2. The method of claim 1 , wherein the first polymer is water soluble.

3. The method of claim 1 , wherein the first polymer is insoluble at low pH and soluble at high pH.

4. The method of claim 3 , wherein the first solvent is water.

5. The method of claim 4 , wherein the first polymer is selected from the group consisting of shellac, poly(meth)acrylates, methacrylic acid-methyl methacrylate copolymers, chitosan, poly beta amino esters, polysaccharides, polysulfonamides, celluloses, polyvinyl acetate phthalate, stearic acid, gelatin, gelatin methacrylate, agarose, hyaluronic acid, collagen, silk, extracellular matrix material, fibrin, hydroxyethyl methyl acrylate, polyethylene glycol, poly(N-isopropylacrylamide), poly(acrylic acid)s, poly(vinyl alcohol), polypeptide-based gels, polyphosphazene gels, poly(propylene fumarate-co-ethylene glycol), and copolymers thereof.

6. The method of claim 1 comprising forming the composite structure on a substrate.

7. The method of claim 1 , wherein the sacrificial material structure or embedding material is a hydrogel.

8. The method of claim 1 , wherein the first solvent is selected from the group consisting of ammonium bicarbonate, borate buffer solution, buffered saline, cell culture media, HEPES buffer, TRIS buffer, water, and sodium bicarbonate solutions.

9. The method of claim 1 , wherein patterning or etching of the sacrificial material comprises a method selected from the group consisting of lithographic patterning, melt-spinning, wet-spinning, electro spinning, spin-coating, three dimensional printing, robotically controlled deposition, and combinations thereof.

10. A method of microfabrication of a composite structure having one or more well defined, reproducible two dimensional and/or three dimensional structures, features, or channels each having sizes between nanometers and centimeters comprising
patterning or etching a sacrificial material formed from a first polymer to form a patterned sacrificial material structure, wherein the patterning or etching of the sacrificial material comprises a method selected from the group consisting of lithographic patterning, melt-spinning, wet-spinning, electrospinning, spin-coating, three dimensional printing, robotically controlled deposition, laser etching, plasma or chemical etching, stereolithography, selective laser sintering, ballistic particle manufacture, fusion deposition modeling, surface micromachining, bulk micromachining, and combinations thereof,
embedding the patterned sacrificial material structure in a polymeric embedding material to form an embedded sacrificial material structure,
wherein the patterned or etched first polymer is insoluble in a first solvent at a first pH and soluble in the first solvent upon a change from the first pH to a second different pH,
contacting the embedded sacrificial material structure with a bath comprising the first solvent at the second different pH; and
wherein the polymeric embedding material is not soluble in the first solvent at the first or at the second different pH, and
removing the solubilized first polymer,
wherein the removal of the first polymer forms the structures, features, or channels, having the pattern of the patterned sacrificial material structure, within the polymeric embedding material.

Assignees

• Bellan Leon M
• Langer Robert S
• Cropek Donald M
• Massachusetts Inst Technology
• Us Army

Inventors

• Bellan Leon M
• Langer Robert S
• Cropek Donald M

Classifications

• C09F1/04 Primary

  Chemical modification, e.g. esterification (resin soaps C11D) · CPC title

• C09D193/02

  Shellac · CPC title

• A61L27/14

  Macromolecular materials · CPC title

• C09D189/06

  derived from leather or skin · CPC title

• A61L27/56

  Porous materials, {e.g. foams or sponges} · CPC title